Encapsulated magnetic particles pigments and carbon black, compositions and methods related thereto

ABSTRACT

Encapsulated particles, such as magnetic particles, colored pigments, or carbon black, with high chemical affinity for ink vehicles. The encapsulated particles of this invention are suitable for printing inks, as well as for magnetic recording systems, such as audio and video tapes and magnetic storage disks, when the encapsulated particles are magnetic particles. The encapsulated particles comprise particles having a coating on their surface, said coating comprising in one embodiment an ionomer and in another embodiment, an oil, such as soya oil, and optionally a thixotropic agent, and/or a binder resin. The method of the present invention for making such encapsulated particles avoids the use of volatile organic solvents and provides printing inks and coating compositions comprising such encapsulated particles, that also avoid the use of volatile organic solvents. Inks may be readily formulated without the need for the complicated and expensive flushing process, by simply dispersing the encapsulated colored pigment or carbon black in the desired vehicle.

This is a divisional of application Ser. No. 08/334,760, filed on Nov.4, 1994, which is a divisional of Ser. No. 07/909,977, filed Jul. 7,1992 now abandoned, which is a continuation-in-part of Ser. No.07/879,936, filed May 8, 1992 abandoned.

FIELD OF THE INVENTION

The present invention relates to the field of magnetic particles,generally, and specifically to the field of encapsulated magneticparticles and applications therefor, such as magnetic recording media,including tapes and discs for storage of sound or data. The presentinvention also relates to the field of printing and inks usefultherefor, generally, as well as specifically to the field oflithographic printing and inks useful therefor. Further, the presentinvention relates to the field of encapsulated pigments and encapsulatedcarbon black, for use in printing inks and other applications, such astoners, coatings and paints.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 5,080,986 relates to a magnetic encapsulated dry tonercomprising a fluorocarbon-incorporated poly(lauryl methacrylate) as corebinder. The capsules shell is either polyurea, polyamide, polyurethane,polyester, or mixtures of thereof, formed by interfacial polymerizationat the oil (capsules)/water (carrier medium) interface. The capsuleswere prepared first in an aqueous medium then spray dried to form thedry toner. The spray drying is an ineffective and costly process, duringwhich capsules, ruptures and/or agglomeration took place. In addition,dry capsules produced by this technique show very low yield.

Brit. Patent No. 1,156,653 relates to a process of encapsulating ironoxide by dispersion polymerization, during which the iron oxide isdispersed in an organic liquid together with a monomer (the monomer issoluble in the organic liquid). Upon polymerization (the polymer isinsoluble in the organic liquid) the polymer precipitates from theorganic liquid, and is absorbed on the surface of the iron oxideparticles.

Brit. Patent No. 950,443 relates to a process to encapsulate iron oxidedispersions in organic solvent with a polymeric skin. The polymeric skinis formed by condensation polymerization.

Encapsulated magnetic particles are also disclosed in U.S. Pat. No.3,627,682. In accordance with that patent, the encapsulating shell wallmaterial is dispersed in a volatile solvent, which solvent is thereafterremoved to form the encapsulated particles. Such an approach isundesirable because it involves the requirement of vaporizing a largeamount of volatile solvent, which is both costly as well as potentiallyinjurious to the environment. U.S. Pat. Nos. 4,420,540, 4,511,629,4,696,859, 4,699,817, 4,713,293, 4,844,991, 5,013,602, and 5,032,428are-directed to magnetic recording media that contain nonencapsulatedmagnetic particles that are dispersed in a binder and then directlyapplied as a dispersion to a substrate, the dispersion also usingvolatile organic solvents.

Offset magnetic printing inks typically use iron oxide pigment as asource for magnetic signals. In order to achieve the required signalstrength, the offset inks should contain a high loading of the ironoxide pigment (40-65% based on the total weight of the ink), but suchhigh loading of iron oxide pigment adversely affects the performances ofthe magnetic printing inks, such as printability, press stability, inktransfer on the roller, ink water balances, drying time, as well as thestability of the magnetic signal.

In addition, the high loading of the iron oxide pigments make itnecessary to pass the ink several passes over the three roll mill, athigh pressure between the rollers, in order to disperse the magneticpigment in the ink's vehicle. The three roll mill does not produce anagglomeration-free magnetic inks, due to the lack of chemical affinitybetween the pigment particles and the ink vehicle. In addition, thismechanical dispersing aid is very costly and time consuming, which addsto the cost of the final ink. Other mechanical dispersing aids, such asa SCHOLD mixer, does not completely eliminate pigment agglomeration.Agglomerations of magnetic iron oxide pigments reduce the magneticsignal strength, and produce an ink with poor runnability on the press.In order to achieve the required signal strength, more inks must beapplied during printing. This in turn increase the press problems of theink and has severe adverse effects on the print quality and the dryingtime.

Surface treatment techniques known in the prior arts do not produce auniformly coated or treated magnetic particle. Performances of magneticink made with the commercially available treated, or untreated, ironoxide are marginal, lacking long run stability and nonreproducible. Theresultant magnetic inks are stiff, short and lack of the proper transferon the ink roller of the printing presses. In addition, the surfacetreatment itself is a very costly process.

Magnetic recording system are usually coated from a solvent baseddispersion of magnetic particles. These dispersion required enormousamount of energy for curing. In addition undesirable air pollutionaccompany such the coating processes.

Encapsulated iron oxide and other magnetic particles for liquid tonerand nonimpact printer applications contain large amounts of solventwhich make them unsuitable for the lithographic printing inks.

From the foregoing it is clear that a significant need exists forencapsulated magnetic particles that may be used in any of theaforementioned application areas, such as printing (lithographic,offset, and the like), magnetic storage (tapes, discs, and the like),and others.

There also exists a significant need for making encapsulated magneticpigments that can be used in the aforementioned application areas, thatdoes not employ the use of volatile organic solvents. Further, such amethod should be able to make encapsulated magnetic particles that havea high percentage of metal in the encapsulated product.

Additionally, there is a need for inks, such as for lithographicprinting, that have a high percentage of encapsulated magnetic particlescontained therein, that are free of volatile organic solvent, and can beemployed without significant agglomeration of the magnetic particles.There is also a similar need for a coating composition for makingmagnetic recording media, wherein the coating composition has a highpercentage of encapsulated magnetic particles contained therein, is freeof volatile organic solvent, and can be employed without significantagglomeration of the magnetic particles.

Additionally, there is a need for a method of making inks that can avoidthe costly preparation steps that are usually required, such as theflushing process that is employed in the manufacture of ink usingflushed pigments or carbon black dispersion.

SUMMARY OF THE INVENTION

The foregoing and other needs are satisfied by the present invention,which, in one embodiment, employs an encapsulation method that does notrequire the presence of organic solvents. Further, the method does notrequire any chemical interaction of the components that encapsulate theparticles (which may be magnetic particles, pigments, or carbon black),and indeed those encapsulation components that form a shell wall aroundthe particles preferably do not chemically react at all. Another aspectof the method of the present invention is that the medium that is usedto disperse the particles (which may be magnetic particles, pigments, orcarbon black) for the purpose of encapsulating the same, actually formsthe shell wall that encapsulates the particles, pigments or carbonblack, fully consuming the dispersing medium as components of the shellwall.

The present invention includes a process of modifying the surfaceproperties of particles (including magnetic particles, such as ironoxide pigments, pigments, or carbon black) to produce hydrophobic (or,in some instances, hydrophilic), encapsulated particles, such asmagnetic particles, pigments or carbon black. Such encapsulatedparticles may be formulated to have high chemical affinity for variousink vehicles, such as lithographic ink vehicles. The encapsulatedmagnetic pigments of this invention are suitable for use in magneticprinting inks, as well as for other magnetic recording systems, such asaudio and video tapes, magnetic storage disks, and other magneticstorage and readable systems.

The encapsulated pigments and carbon black may be used to form inks,such as those used in lithographic (direct and offset), letterpress,gravure, flexographic, silk-screen, and mimeograph printing processes,or to form radiation curable inks, such as infrared and ultravioletcurable inks.

The encapsulated pigments and carbon black also may be used asphotoconductive particles, electrically conductive particles,hydrophobic/hydrophilic particles, toners to develop latent images, andcolorants in coatings and paints.

In accordance with one aspect of the present invention, there isprovided a coated particle (which may be a magnetic particle, pigment,or carbon black) having a particle diameter from about 0.1 to about 100microns, typically from about 0.5 to about 5 microns, and having acoating on its surface, said coating comprising an ionomer. The coatingmay also comprise an oil, a thixotropic agent, and/or a binder resin.

A unique aspect of the present invention is the fact that the coating onthe encapsulated particles most preferred is very firmly associated withthe particle itself. This is due to the presence of an ionomer in thepreferred encapsulating wall materials. The ionomer is critical toobtain the best functional properties for the inks.

Another unique aspect of the present invention is the ability to usesoya oil in the encapsulating wall material. The soya oil isinexpensive, yet may be readily incorporated into the shell. Thepresence of the soya oil provides for excellent compatibility betweenthe encapsulated particles and, for example, ink vehicles, such as thoseused in many printing processes. Further, the presence of the soya oilin the encapsulating wall specifically provides for the ability toincorporate soya oil into the ink vehicle, which results in a formulatedink product that is relatively inexpensive, but moreover, isecologically more acceptable than ink formulations that contain a largeamount of volatile organic solvent.

The inks of the present invention, when the ionomer is employed, havegreatly improved properties over conventional inks. Even when no ionomeris employed in the encapsulating shell, inks made with the particles ofthe present invention still exhibit improved functional properties overconventional ink formulations.

The soya oil has excellent wetting characteristics for the pigmentsurface. However, the soya oil has an adverse effect on the drying timeof the inks, the more soya oil content in the printing inks, the worsethe drying time of that ink.

According to the current invention, the soya oil was modified by theincorporation of ionomers, polymers, resins, thixotropic agents and itis possible now to increase the soya content to high level (25% in someinstances).

There is also provided a printing ink, such as a lithographic printingink comprising a (lithographic) printing ink vehicle and from about 1 toabout 99 percent, typically about 1 to about 90 percent, of encapsulatedparticles (which may be magnetic particles, pigments, or carbon black),based on the total weight of the ink, said ink being free of volatileorganic solvents. Preferably, the vehicle contains a vegetable oil, suchas soya oil, or a derivative thereof.

A method for encapsulating particles (which may be magnetic particles,pigments, or carbon black) is also provided. As indicated previously thepresent invention provides an encapsulation method that comprisesdispersing the particles in a heated medium that comprises all of thecomponents for forming a shell wall around the particles, without thepresence of any volatile organic solvent, and cooling the dispersion toallow the components of the medium to solidify to form the shell wall toencapsulate the particles, fully consuming the dispersing medium ascomponents of the shell wall, to form the desired encapsulatedparticles.

In a specific embodiment, the method comprises forming a melt comprisinga polymer, an ionomer, and an oil and resinous material, dispersing saidparticles in said melt, and allowing said dispersion to cool, said meltbeing free of volatile organic solvents and said melt being present inan amount from about 10 to about 80 percent, based on the total weightof the encapsulated product. The melt may also comprise an oil, athixotropic agent, and/or a binder resin.

In another embodiment, the melt will comprise an oil, such as avegetable oil, preferably soya oil, and resinous material.

A composition for use in forming a magnetic recording medium is alsoprovided, wherein the composition comprises a dispersion of encapsulatedmagnetic particles in a resinous carrier, said particles beingencapsulated with a composition comprising an ionomer.

A magnetic recording medium comprising a nonmetallic support and ametallic layer formed thereon that is comprised of a compositioncomprising encapsulated magnetic particles and a resinous binder,wherein the magnetic particles have been encapsulated with a coatingcomprising an ionomer, is also provided.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

THE OIL

The oil may be any suitable hydrocarbon that will act as a good mediumfor the other shell wall components in their heated state. Preferablythe oil is a vegetable oil, especially soya oil. Other suitable oilsinclude linseed oil or any other vegetable oil (cotton seed, china wood,and the like). Common derivatives of such oils, such as wholly orpartially hydrogenated oils or derivatives of such oil may be used. Bothraw and treated (heat, alkali, acid, . . . etc.) oils are applicable tothe current invention.

THE THIXOTROPIC AGENT

The thixotropic agent may be any agent preferably a polymeric component,that is solid at 25° C. but will melt without degrading at a temperatureof about 150° C, or lower. Preferably the thixotropic agent, will imparthydrophobicity to the pigment particles as well as thixotropicproperties when the particles are used in a final magnetic offsetprinting inks. Most preferably the thixotropic agent is an oxidizedpolyethylene homopolymer. Other useful thixotropic agents includegellants and polyethylene gel.

Most preferably the thixotropic agent will have an acid value from about6 to about 120 and will have the similar acid number as for the binder.Useful thixotropic agents include those available from Allied Signalunder the trademarks A-C 316, 316A, 325, 330, 392, 395, 395A, 629, 629A,655, 656, 680 and 6702, especially A-C 629A.

THE BINDER RESIN

The binder resin may be any agent preferably a polymeric component, thatis solid at 25° C. but will melt without degrading at a temperature ofabout 150° C., or lower. The binder resin is preferably a maleicmodified rosin ester (trademark Beckacite 4503 resin from Arizonachemical company). Other useful binder resins include phenolics,maleics, modified phenolics, rosin ester, and modified rosin, phenoticmodified ester resins, rosin modified hydrocarbon resins, hydrocarbonresins, terpene phenotic resins, terpene modified hydrocarbon resins,polyamide resins, tall oil rosins, rosin ester resins, polyterpeneresins, hydrocarbon modified terpene resins, acrylic and acrylicmodified resins and similar resins or rosin known to be used in printinginks, coatings and paints.

THE PIGMENTS

The pigments that are of use in the present invention include but arenot limited to the following:

Metallized Azo Reds: Red 49:1 (Barium salt), Red 49:2 (Calcium salt),Red 63:1 (Calcium salt)

Toluidine reds:

Naphthol reds

Pyrazolones

Rhodamines

Quiacridones: Red B, Red Y, Magenta B, Magenta and violet

Phthalocyanine blues

Phthalocyanine greens

Carbazole violets

Monoarylide Yellow

Diarylide Yellow

chrome yellow

Red Lack C

nithol reds: calcium and barium salts

Lithol rubine

Bon Maroon

Perylene pigments

red 2B: Calcium, Barium and Magnesium salts

Chrome Yellow

Chrome Orange

Molybdate orange

Orange 36, Diarylide orange, Dianisidine orange, tolyl orange andDinitraniline orange

Such pigments may have a wide range of particle sizes, as from about 0.1μm to about 100 μm, preferably from about 0.2 μm to about 5 μm, and morepreferably from 0.2 to 2 μm.

THE METAL PARTICLES

The magnetic metal particles of use in the present invention are usuallyiron oxide, such as cubic iron oxide, accicular iron oxide, gamma-Fe₂O₃, and mixed crystals of gamma-Fe₂ O₃ and Fe₃ O₄. The particles alsomay be, however, Cr₂ O₂, gamma Fe₂ O₃ or Fe₃ O₄ coated with cobalt,barium ferrite, iron carbide, pure iron, and ferromagnetic alloy powderssuch as Fe--Co and Fe--Co--Ni alloys. The particle size should be fromabout 0.1 microns to about 100 microns, typically from about 0.2 toabout 5 microns, preferably from about 0.2 to about 2 micron.

A preferred metal particle is Type 031182 magnetic pigment from WrightIndustries, Inc., Brooklyn, N.Y. having a particle size of 0.7 microns.

THE IONOMERIC COMPONENT

As indicated, in a preferred aspect of the present invention, anionomeric composition is employed. The ionomeric composition containsionomers that have a melting point of at least about 70° C. The ionomersare critical to obtain the best functional properties of inks made withthe encapsulated particles.

Typically, ionomers contain a certain number of inorganic salt groupsattached to a polymer chain, such as up to 15 mol % ionic groups pendantto a base polymer, such as a hydrocarbon or perfluorinated polymerchain.

The pendant ionic groups interact to form ion-rich aggregates containedin a nonpolar polymer matrix. The resulting ionic interactions stronglyinfluence polymer properties and application. The salt groups chemicallycombined with a nonpolar polymer backbone have a dramatic influence onpolymer properties not observed with conventional homopolymers or withcopolymers based on nonionic species. The ionic groups interact orassociate to form ion-rich regions in the polymer matrix.

The ionic interactions and resultant polymer properties are dependent onthe type of polymer backbone (plastic or elastomer); ionic functionality(ionic content), generally 0-15%; type of ionic moiety (carboxylate,sulfonate, or phosphonate); degree of neutralization (0-100%); and typeof cation (amine, metal, monovalent, or multivalent).

An ionomer can be defined as a polymer composed of a polymeric backbonecontaining a small amount of pendant carboxylic acid sulfonate orphosphate groups, usually less than 15 mole percent, which areneutralized, partially or completely, to form an ionomer. Ionichydrocarbon polymers for elastomers or plastics are disclosed in U.S.Pat. No. 3,264,272.

Ionomers may be prepared by copolymerization of a functionalized monomerwith an olefinic unsaturated monomer or direct functionalization of apreformed polymer. Typically, carboxyl-containing ionomers are obtainedby direct copolymerization of acrylic or methacrylic acid with ethylene,styrene, and similar comonomers by free-radical copolymerization. Theresulting copolymer is generally available as the free acid, which canbe neutralized to the degree desired with metal hydroxides, acetates,and similar salts.

Another route to ionomers involves modification of a preformed polymer.Sulfonation of polystyrene, for example, permits the preparation ofsulfonated polystyrene (S-PS) with a content of sulfonic acid groups inproportion to the amount of sulfonating agent. Such reactions may beconducted in homogeneous solutions, permitting the direct neutralizationof the acid functionality to the desired level. The neutralized ionomermay be isolated by conventional techniques, i.e., coagulation in anon-solvent, solvent flashing, etc.

Useful ionomers include:

    ______________________________________                                        poly(ethylene-co-acrylic acid)                                                                       Aclyn ®                                            poly(ethylene-co-methacrylic acid)                                                                   Surlyn ®                                           poly(butadiene-co-acrylic acid)                                                                      Hycar ®                                            perfluorosulfonate ionomers                                                                          Nafion ®                                           perfluorocarboxylate ionomers                                                                        Flemion ®                                          telechelic polybutadiene                                                                             Hycar ®                                            sulfonated ethylene-propylene                                                                        Ionic                                                  terpolymer             Elastomer ®                                        poly(styrene-co-acrylic acid)                                                 sulfonated polystyrene                                                        sulfonated cetyl elastomer                                                    sulfonated polypentenamer                                                     ______________________________________                                    

Ionomers of use in the present invention may be made by first forming afunctional polymer. Useful polymers include acrylic copolymers,polyester-acrylic graft copolymers, polyester polymers and urethanepolymers.

Useful acrylic copolymers are carboxyl functional acrylic copolymerswhich can be produced by polymerizing monomers in bulk, in an organicsolvent, or by other suitable processes to produce carboxylic functionalpolymer. The carboxylic acid functional acrylic copolymer comprisescopolymerized ethylenically unsaturated monomers, including ionizablecarboxyl monomers, to produce a copolymer containing reactive primarycarboxylic acid groups and having a number average molecular weightbetween 500 and 100,000, and preferably between 1,000 and 40,000. Numberaverage molecular weights are typically measured by GPC according toASTM methods such as D3016-72; D3536-76; D3593-80; or D3016-78.

The acrylic copolymers have a Tg between 20° C. and 100° C. ascalculated by the FOX equation based on the weight ratio of specificmonomers. The Acid No. of the carboxylic acid functional polymer isbetween 10 and 200 and preferably is between 30 and 90. The copolymerscan be produced by bulk, solvent, or suspension polymerization ofethylenically unsaturated monomers including carboxylic acid monomers,activated by peroxide or azo or other free radical initiator atpolymerization temperatures typically between 40° C. to 170° C. andpreferably between 70° C. to 150° C. Typically 0.2% to 5% peroxideinitiator is utilized based on the weight of the monomers. Typicalpolymerization initiators can include for instance benzoyl peroxide,t-butyl hydroperoxide, tertiary butyl perbenzoate, cumene peroxide andsimilar peroxide polymerization catalysts which are preferred. Otherinitiators include azo initiators such as azobisisobutyronitrile andpersulfate or ammonium persulfates. Molecular weight control can beachieved by adjusting temperature, initiator level, or by the additionof chain transfer agents, such as the common mercaptans.

Typical solvents useful in preparing the organic solvent-borne acryliccopolymers can include for instance, xylene, toluene, ethyl acetate,acetone, methylisobutyl ketone, methyl n-amyl ketone, methylisoamylketone, ethylamyl ketone, amyl acetone, mathylethyl ketone, ethylalcohol, mineral spirits, ethylene glycol monoethyl ether acetate, andother aliphatic, cycloaliphatic and aromatic hydrocarbons, esters,ethers, ketones and alcohols. After the polymerization is completed, thesolvents may be stripped off to produce a solid polymer for use in apowder coating.

Copolymerizable ethylenically unsaturated monomers useful in producingthe carboxylic acid functional acrylic copolymer are monomers containingcarbon-to-carbon, ethylenic unsaturation and include vinyl monomers,acrylic monomers, allylic monomers, acrylamide monomers, and mono- anddicarboxylic unsaturated acids. Vinyl esters include vinyl acetate,vinyl propionate, vinyl butyrates, vinyl benzoates, vinyl isopropylacetates and similar vinyl esters. Vinyl halides include vinyl chloride,vinyl fluoride, and vinylidene chloride. Vinyl aromatic hydrocarbonsinclude styrene, methyl styrenes and similar lower alkyl styrenes,chlorostyrene, vinyl toluene, vinyl naphthalene, divinyl benzoate, andcyclohexene. Vinyl aliphatic hydrocarbon monomers include alpha olefinssuch as ethylene, propylene, isobutylene, and cyclohexene as well asconjugated dienes such as 1,3 butadiene, methyl-2-butadiene,1,3-piperylene, 2,3 dimethyl butadiene, isoprene, cyclopentadiene, anddicyolopentadiene. Vinyl alkyl ethers include methyl vinyl ether,isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether.Acrylic monomers include monomers such as lower alkyl esters of acrylicor methacrylic acid having an alkyl ester portion containing between 1to 12 carbon atoms as well as aromatic derivatives of acrylic andmethacrylic acid. Useful acrylic monomer include, for example, acrylicand methacrylic acid, methyl acrylate and methacrylate, ethyl acrylateand methacrylate, butyl acrylate and methacrylate, propyl acrylate andmethacrylate, 2-ethyl hexyl acrylate and methacrylate, cyclohexylacrylate and methacrylate, decyl acrylate and methacrylate,isodecylacrylate and methacrylate, benzyl acrylate and methacrylate, andvarious reaction products such as butyl, phenyl and cresyl glycidylethers reacted with acrylic and methacrylic acids, hydroxyl alkylacrylates and methacrylates such as hydroxyethyl and hydroxypropylacrylates and methacrylates, as well as amino acrylates andmethacrylates.

The carboxylic acid functional polymer comprises copolymerized monomersincluding at least 1% by weight ionizable carboxylic acid monomer whichinclude acrylic and methacrylic acids as well as olefinic unsaturatedacids. Acrylic acids include acrylic and methacrylic acid, ethacrylicacid, alpha-chloracrylic acids, alpha-cyanoacrylic acid, crotonic acid,and beta-acryloxy propionic acid. Olefinic unsaturated acids includefumaric acid, maleic acid or anhydride, itaconic acid, citraconic acid,mesaconic acid, muconic acid, glutaconic acid, aconitic acid,hydrosorbic acid, sorbic acid, alpha-chlorosorbic acid, cinnamic acid,and hydromuconic acid. On a weight basis, the carboxylic acid functionalpolymer contains at least 1% copolymerized carboxyl functional monomersand preferably between 5% and 15% carboxylic acid monomers.

Polyester polymers comprise the esterification products of glycols,diols, or polyols with excess equivalents of dicarboxylic acid orpolycarboxylic acids. Linear aliphatic glycols are esterified withgreater molar amounts of aromatic dicarboxylic acid and/or linearsaturated dicarboxylic acid having between 2 and 36 linear carbon atomssuch as adipic, azelaic, succinic, glutaric, pimelic, suberic or sebacicacid to produce low molecular weight polyesters. Commercially availablelinear saturated dicarboxylic acids are dodecanedioic acid, dimer fattyacids, or azelaic acid. Aromatic dicarboxylic acids (anhydrides) includephthalic, isophthalic, terephthalic, and tetrahydrophthalic. Minoramounts of polyfunctional acids such as trimelletic acids can be added.Suitable glycols include linear aliphatic glycols having 2 to 16 carbonatoms such as 1,3- or 1,4-butylene glycol, 1,6-hexane diol, neopentylglycol, propylene glycol, ethylene glycol and diethylene glycol,propylene, and dipropylene glycol, and similar linear glycols,hydrogenated Bisphenol A. Minor amounts of polyols can be used such asglycerol, pentaerythritol, dipentaerythritol, or trimethylol ethane orpropane. The molar deficiency of the glycol over the greater molaramounts of aromatic and linear saturated dicarboxylic acid is betweenabout 1% and 50%. Hence, the polyester may contain an excess ofunreacted carboxylic groups to provide a carboxyl polyester having anAcid No. between 5 and 300. The molecular weight of useful polyesterpolymers are between 500 and 50,000 and preferably between 1,000 and10,000. Glycol can be esterified with minor amounts of up to about 20%by weight of unsaturated dicarboxylic acids (anhydrides) includingmaleic, fumaric or itaconic acids; or monocarboxylic acids such asacetic, benzoic, and higher chain aliphatic acids up to about 12 carbonatoms as well as aromatic acids. The polyester component can be producedby solvent or bulk polymerization although bulk polymerization ispreferred. The raw materials can be charged in bulk and esterificationpolymerized at temperatures typically between 170° C. to 240° C.although moderately higher or lower temperatures can be utilizedsatisfactorily. Azeotropic removal of water with a suitable solvent,such as xylene, often helps to reduce processing times. Anesterification catalyst can be used, typically at less than 1% levelsbased on charge, such as an organic tin compound.

Grafted copolymers of polyester and acrylics can be produced byfree-radical polymerization of ethylenically unsaturated monomers,including acrylic and carboxyl monomers, in the presence of a preformedmolten or fluid polyester at temperatures sufficient to induce additioncopolymerization of the monomers along with some grafting onto thepolyester backbone. Organic solvents are not required, but can be addedif desired to provide desired viscosity in solvent coatings. On a weightbasis, the polyester-acrylic graft polymer may contain between 5% and90% polyester polymer component with the balance being the acrylicpolymer component. The polyester component of the polyester acrylicgraft polymer is a moderate molecular weight polymer having a numberaverage molecular weight between about 500 and 50,000 and preferablybetween 1,000 and 5,000. The polyester polymer should have an Acid No.above about 5, preferably between 20and 100, and can be prepared aspreviously described.

The acrylic polymer component of the polyester-acrylic graft polymercomprises in-situ copolymerized ethylenically unsaturated monomers,including acrylic monomers and carboxyl monomers, along with other ethylwith other ethylenically unsaturated monomers if desired. Acrylicmonomers include monomers such as lower alkyl esters of acrylic ormethacrylic acid having an alkyl ester portion containing between 1 to12 carbon atoms as well as aromatic derivatives of acrylic andmethacrylic acid. Useful acrylic monomers include, for example, acrylicand methacrylic acid, methyl acrylate and methacrylate, ethyl acrylateand methacrylate, butyl acrylate and methacrylate, propyl acrylate andmethacrylate, 2-ethyl hexyl acrylate and methacrylate, cyclohexylacrylate and methacrylate, decyl acrylate and methacrylate,isodecylacrylate and methacrylate, benzyl acrylate and methacrylate, andvarious reaction products such as butyl, phenyl, and cresyl glycidylethers reacted with acrylic and methacrylic acids, hydroxyl alkylacrylates and methacrylates such as hydroxyethyl and hydroxypropylacrylates and methacrylates, as well as amino acrylates andmethacrylates. Acrylic acids include acrylic and methacrylic acid,ethacrylic acid, alpha-chloracrylic acid, alpha-cyanoacrylic acidcrotonic acid, beta-acryloxy propionic acid, and beta-styryl acrylicacid. Other ethylenically unsaturated monomers have been previouslydescribed herein. The copolymerized monomers for the acrylic componentof the polyester-acrylic graft polymer comprises copolymerized monomers,on a weight basis between 1% and 100 of acrylic monomer, between 0% and30% acrylic or methacrylic. carboxylic acid monomer, with the balancebeing other ethylenically unsaturated monomers. Preferred acryliccomponents comprise between 20% and 90% acrylic monomer, between 5% and15% carboxyl acid monomer, with the balance being other ethylenicallyunsaturated monomers. It should be noted that the carboxyl functionalitycan be part of the polyester polymer or part of the grafted acrylicpolymer or on both polymers. The Acid No. of the polyester-acrylic graftpolymer is preferably between about 20 and 100. The polyester-acrylicgraft polymer preferably comprises by weight between 5% and 90%polyester polymer component and between 10% and 95% acrylic polymercomponent. The number average molecular weight of the polyester-acrylicgraft polymer is between about 2,000 and 100,000 while preferredmolecular weights are between 5,000 and 50,000 as measured by GPC. GPCchromatograms of the polyester and the grafted polyester-acrylicindicated that good grafting efficiency can be obtained.

Urethane ionomers can be produced with terminal carboxyl groups as wellas terminal blocks, which can be crosslinked by zinc organic salts uponheating in accordance with this invention.

Carboxyl functional urethanes can be produced by coreactingdiisocyanates with a diol or a polyol and a hydroxyl acid. Linearpolyurethanes are obtained from difunctional reactants while branchedpolyurethanes are produced from the combination of difunctional andhigher functional reactants Urethanes can be prepared from any ofseveral available aromatic, aliphatic, and cycloaliphatic diisocyanatesand polyisocyanates. Suitable polyisocyanates can be di- ortriisocyanates such as, for example, 2,4- and 2,6-tolylenediisocyanates, phenylene diisocyanate; hexamethylene or tetramethylenediisocyanates, 1,5-naphthalene diisocyanate ethylene or propylenediisocyanates. Trimethylene or triphenyl or triphenylsulfonetriisocyanate, and similar di- or triisocyanates or mixtures thereof.The polyisocyanate can be generally selected from the group ofaliphatic, cyclo-aliphatic and aromatic polyisocyanates such as forexample hexamethylene 1,6-diisocyanate, isophorone diisocyanate,diisocyanate, 1,4-dimethyl cyclohexane, diphenylmethane diisocyanate2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof,polymethylene polyphenyl polyisocyanate, or isocyanate functionalprepolymers.

A wide variety of diols and polyols can be used to prepare urethaneswith a wide range of properties. Polyethers, such as thepolytetramethylene oxides can be used to impart flexibility as well asthe polyethylene oxides and polypropylene oxides. Simple diols that canbe used include neopentyl glycol, 1,6-hexane diol, and longer chaindiols having 12, 14 and higher carbon chains. Branching can beintroduced with polyols such as trimethylol propane and pentaerythritol.Hydroxyl functional polyesters and various other hydroxyl functionalpolymers are also suitable. Useful polyols preferably contain two,three, or four hydroxyl groups for coreaction with the free isocyanategroups. Useful polyols are: -diols such as ethylene glycol, propyleneglycols, butylene glycols, neopentyl glycol, 14-cyalohexane dimethanol,hydrogenated hisphenol A, etc.; triols such as glycerol, trimethylolpropane, trimethylol ethane; tetrols such as pentaerythritol; hexolssuch as sorbitol, dipentaerythritol, etc.; polyether polyols produced bythe addition of alkylene oxides to polyols; polycaprolactone polyolsproduced by the addition of monomeric lactones to polyols, such ascaprolactone; and hydroxyl terminated polyesters.

The polyurethane also contains a coreacted hydroxy-acid material. Thehydroxy-acid contains at least one reactive hydroxy group for coreactingwith the isocyanate during polymer synthesis and at least one carboxygroup which is essentially non-reactive to the isocyanate groups duringthe polymer synthesis. Examples of alkyl acids are 2,2-dihydroxymethylpropionic acid, 2,2-dihydroxymethyl butyric acid, glycolic acid, and thelike; other acids are lactic acid, 12-hydroxy stearic acid, the productof the Dieis-Alder addition of sorbic acid to di-(2-hydroxyethyl)maleate or fumarate, or low molecular weight (300 to 600) precondensatesof polyols with tribasic acids such as trimelletic anhydride orRicinoleic acid. Acid functionality can be introduced with materialslike 12-hydroxystearate, dimethylolpropionic acid, and various otherhydroxy acids as well as carboxylated polyesters such as the NiaxPWB-1200 (Union Carbide). Monohydroxyl acids will place the acidfunctionality at the end of the chain, while the diol acids willrandomly place the acid groups in the chain. When isocyanates arereacted with diols and polyols of various types, the reaction rate maybe enhanced by the use of catalysts. Common isocyanate catalysts aresuitable and examples include dibutyltindilaurate, dibutyltinoxide, andthe like.

The number average molecular weight of the urethane can be between 500and 100,000 and preferably between 5,000 and 50,000 as measured by GPC.

In accordance with this invention, the useful level of neutralization ofthe carboxylic acid functional copolymer, is above 10% and preferablybetween 30% and 200% and most preferably between 50% and 150%neutralization. Neutralization with a basic sodium composition, such assodium hydroxide, is preferred, so that the ionomer contains sodium ionsas the cationic component.

Useful ionomers include those available under the trademarks ACLYN 260to 286 and 260A to 286A, which are ethyleneacrylic and sodium ionomers,with molecular weights of over 1200. These ionomers are available withCa, Mg, Na, and Zn cations. Especially preferred is ACLYN 276A.

THE INKS

The encapsulated pigment may be added to an ink vehicle, such as avehicle typically used for lithographic (direct and offset),letterpress, gravure, flexographic, silk-screen, or mimeograph printingprocesses, or vehicles used to form curable inks, such as. infrared andultraviolet curable inks, to form a printing ink. Generally theencapsulated pigments will be present in an amount from about 1 to about90percent, preferably from about 40 to about 85, and most preferablyfrom about 50 to about 80 percent, based on the total weight of the ink.Any suitable ink vehicle may be used. The full advantage of the presentink formulations is achieved only if the vehicle is substantially freeof volatile organic solvent. As used herein the term volatile organicsolvent is meant to indicate such solvents that are vapors attemperatures above about 120° C. Preferably, the ink vehicle willinclude one or more vegetable oils, as defined previously, especially asoya oil.

One ink vehicle that is preferred is a vehicle made from 16-V-10 varnish(Sun Chemical), varnish #4895 (100% solid varnish made from hydrocarbonresin, Superior Varnish), varnish #6948 (100% solid soya gel varnish,Superior Varnish Co.). The mixture may be allowed to mix, as by using aSCHOLD mixer, for mixing time from about 1 to about 4, preferably fromabout 1 to about 2 hours. Such inks exhibit excellent transfer, veryfast drying, high signal strength at thinner ink film, long runstability without emission of any hazardous solvent, and produce highquality prints.

THE ENCAPSULATION METHOD

According to the present invention the encapsulated particles areprepared by dispersing particles of the specified size, such as amagnetic powder, preferably untreated, hydrophilic cubic iron oxide(black magnetic ink pigment trade code 031181 from Wright IndustriesInc.) into preheated shell wall former materials, as by the aid of aSCHOLD mixer. The shell wall material preferably contains an oil,preferably a soybean oil (Kerely Ink), a binder resin, preferably amaleic modified rosin ester (trademark Beckacite 4503 resin from Arizonachemical company), a thixotropic agent, preferably an oxidizedhomopolymer polyethylene gel (AC629A polyethylene from Allied-SignalInc.) and an ionomer, preferably an ethylene acrylic acid ionomer,preferably sodium ionomer (trademark Aclyn A 276 from Allied signal).

The shell wall materials are heated to a temperature just above theirsoftening point (i.e. 140-150° C. ). The heating is accompanied withconstant mixing until all the ingredients are melted and dissolved inthe carrier, such as soybean oil. At this stage the particles, such asiron oxide pigment, i.e. the capsules core materials, are addedportion-wise to the hot shell wall materials while maintaining theconstant stirring. After the completion of the addition of theparticles, the mixture is allowed to be mixed until a homogeneous,uniform dispersion of the iron oxide pigments in the host hot shell wallforming materials is achieved. Finally the mixture is allowed to cool tothe room temperature. Upon cooling the System, the shell wall materialssolidify and encapsulate the particles with a (hydrophobic) shell. Atoning blue pigment, such as an alkali blue may be added to theparticles, such as iron oxide core materials, to improve the color ofthe printed ink, when the encapsulated particles are used as a printingink.

Similar method was used to encapsulate colorants and carbon black.

The weight percentage compositions of the encapsulated particles aregenerally in the following ranges:

    ______________________________________                                        Oil                  from 10 to 90                                            Preferably           from 5 to 75                                             Most Preferably      from 10 to 55                                            Resins               from 0 to 50                                             Preferably           from 1 to 35                                             Most Preferably      from 2 to 20                                             Thixotropic Agent    from 0 to 25                                             Preferably           from 0.1 to 15                                           Most Preferably      from 0.2 to 10                                           Ionomer              from 0 to 20                                             Preferably           from 0.1 to 15                                           Most Preferably      from 0.1 to 10                                           Core Materials       from 1 to 90                                             Preferably           from 5 to 85                                             Most Preferably      from 10 to 80                                            Dye                  from 0 to 15                                             Preferably           from 0.5 to 10                                           Most Preferably      from 1 to 6                                              NB                                                                            ______________________________________                                    

These ranges are for magnetic, pigments, and carbon blacks.

Typically, then, the coating will comprise from about 10 to about 80percent of the coated particle. All of the foregoing percentages are byweight, based on the total weight of the encapsulated magnetic particle.

MAGNETIC RECORDING MEDIA

It is typical for magnetic recording media, such as tapes and discs, tobe made by applying a magnetic coating to a substrate, typically apolymeric substrate, and most typically a polyethylene terephthalicfilm. The magnetic particles of the present invention may be applied toa suitable substrate to form a magnetic recording medium by manners wellknown in the art. For example, the particles may be dispersed in asuitable binder, such as vinyl chloride/vinyl acetate copolymers, vinylchloride/vinyl acetate/vinyl alcohol polymers, vinyl chloride/vinylidenechloride copolymers, polyurethane resins, polyester resins,acrylonitrile/butadiene copolymers, nitrocellulose, cellulose acetatebutyrate, epoxy resins, and acrylic resins.

Thus, the present invention provides a magnetic recording mediumcomprising a nonmetallic support and a metallic layer formed thereonthat is made of a composition comprising magnetic particles and aresinous binder, wherein the magnetic particles have been encapsulatedin accordance with the present invention.

The magnetic recording media made in accordance with the presentinvention may exhibit extremely good signal to noise characteristics.This should be achievable in view of the fact that the encapsulatedmagnetic particles of the present invention are very uniform in size andproperties, and can be deposited in an extremely uniform manner onto asubstrate, without agglomeration of the particles. The resulting coatingshould be very smooth and abrasion resistant, giving rise to long usefullives for the recording media.

GENERAL

The advantages of the current invention over the prior art include:

1. The inks, including magnetic inks, made according to the currentinvention show excellent functional properties as compared with thosemade of identical pigments which have not been treated. Inks madeaccording to the current invention show the following improvements, overthe prior art magnetic inks: fast ink drying, excellent transfer on thepress, high signal strength at thinner ink film, open on the press,excellent signal stability, excellent press stability, and excellentshelf life.

2. The fast drying properties of the ink allow the printer to convertthe printed materials into final products immediately after printing,which cannot be achieved with prior art compositions, even with thosecontaining auxiliary driers. Higher throughput can therefore be achievedwith the current invention.

3. The fast drying property of the ink made according to the currentinvention was achieved without the use of the auxiliary driers. Thishelps to keep the ink open on the press for a very long period of time.

4. The fast drying may be achieved in air and without any externalenergy source such as heat, UV radiation, or IR radiation.

5. The ink is environmentally safe. No undesirable solvents or volatilevapors are emitted during its application.

6. Manufacture of the encapsulated particles, such as magnetic pigments,of the current invention does not contribute to air pollution, as novolatile solvents are used during the manufacturing process.

7. The magnetic inks produce according to the current invention exhibitvery high signal strength, even with thin ink films, as compared withthose of the prior art.

8. The high signal strength is achieved by enhancing the chemicalaffinity between the encapsulated magnetic pigments and the bindersystem.

9. The encapsulated particles are found to disperse very easily in thebinder system, to produce an agglomeration-free magnetic dispersion.

10. The current invention produces uniform, agglomeration-freeencapsulated particles. Hence, when magnetic particles are encapsulated,stronger signal strength at thinner film, with superior pressperformances, as compared to prior art of treated or untreated magneticpigments are achieved.

11. The encapsulated particles, such as colored pigments and magneticparticles, are chemically compatible with ink vehicles, such aslithographic and letter press ink vehicles. The need for the expensiveand time consuming three roll mill during manufacturing the magneticinks are eliminated. A simple mixing process is sufficient to produce anink with zero fines of grind.

12. The final products of the encapsulated particles are 100% solid. Nohydrocarbon solvent, or external liquids are use as a a carrier liquidduring the encapsulation process.

13. The capsules constitute 100% of the encapsulating system.

14. The hot shell wall materials act as a carrier for the encapsulationas well as a wall former materials.

15. The encapsulation process imparts the necessary hydrophobicproperties to the particles, such as magnetic particles. This is animportant property for offset printing inks to achieve a proper inkwater balance and to prevent ink emulsification during printing onpresses equipped with either an integrated or segregated dampeningsystem.

16. The core material may constitute up to 90%, by weight, of the totalweight of the capsules.

17. The surfaces of the particles, such as iron oxide, and the shellwall materials are chemically compatible. Hence, the surface of theparticles are efficiently wetted with the hot shell wall materials. Thissignificantly enhances the pigment dispersion in the carrier medium andprevents pigment agglomerations.

18. Simple mechanical mixing produces a very uniform dispersion ofparticles, such as iron oxide, in the host shell wall materials.

19. The shell wall materials may constitute soybean oil, maleic modifiedrosin ester, polyethylene gellant and sodium ionomer.

20. The hot shell wall materials, when cooled, quickly solidify andencapsulate the highly dispersed particles. The shell wall, especiallywhen ionomers are present, adheres strongly to the surface of theparticles and becomes indistinguishable parts of it.

21. The shell wall adheres strongly on the surfaces of the iron oxidepigments.

22. The ionomers (especially the sodium ionomer) enhance pigmentdispersion in the hot shell wall materials, promote the adhesion of theshell wall materials on the surfaces of the magnetic particles, controlviscosity and control the hydrophobic/hydrophilic characteristic of thefinished inks, and promote the adhesion of the finished ink on thesubstrate.

23. The gellants (especially the oxidized polyethylene homopolymer)impart hydrophobicity for the pigment particles as well as thixotropicproperties to the final magnetic offset printing inks.

24. The maleic modified rosin ester promotes the chemical affinitybetween the encapsulated magnetic pigments and the host printing inkvehicles, and enhances ink setting and drying properties of the inks.

25. The encapsulated carbon black and colored pigments according to thecurrent invention are much safer and easier to handle than the priorart's pigments and carbon black.

26. The current invention eliminates the hazardous dusting problemsduring weighing or packaging of the magnetic particles, pigments andcarbon blacks.

27. The high pigment to ink vehicle ratio is achieved according to thecurrent invention, without affecting the excellent press performance ofthe ink.

28. The encapsulated magnetic pigment according to the current inventionmay contain cubic iron oxide or accicular iron oxide pigments.

The present invention also provides a means for making inks byencapsulating the desired pigment or carbon black in accordance with thepresent invention, then dispersing the encapsulated pigment or carbonblack in the desired vehicle. The vehicle may be one suitable forlithographic, letterpress, gravure, or flexographic printing, or for useas a radiation curable ink. By use of the encapsulated pigments andcarbon blacks of the present invention, particle agglomeration iseffectively eliminated.

Because the encapsulated pigment or carbon black has a strong affinityfor the ink vehicles (varnishes), the encapsulated particles are easilydispersed into the desired vehicle, to form agglomerate-free printinginks. Because of the high affinity of the encapsulated particles withrespect to the ink vehicles, it is possible to achieve very high pigmentloadings, such as up to 90 percent, by weight. Such is in sharp contrastto the flushing process of the prior art in which a presscake ofcolorants is dispersed in an oleoresinous binder, using a mechanicalaid, such as a three roll mill. The process requires the complicated useof hydrocarbon solvents, grinding vehicles, surfactants, and varnishes.Auxiliary driers and/or energy is often required, depending upon theflush and ink vehicles. The resultant compositions is very viscous anddifficult to handle, even though the pigment loading is relatively low,usually not above 50 to 55 percent. All such problems are eliminated byuse of the present invention.

The invention will be further illustrated in terms of the followingnonlimiting examples.

EXAMPLES

The general method utilized to prepare the encapsulated particles isdescribed below:

According to the present invention the encapsulated particles areprepared by dispersing the untreated, particles, such as hydrophiliccubic iron oxide (black magnetic ink pigment trade code 031182 fromWright Industries Inc.) into preheated shell wall former materials, asby the aid of a SCHOLD mixer. The shell wall material contains soybeanoil (Kerely Ink), a maleic modified rosin ester (trademark Beckacite4503 resin from Arizona chemical company), an oxidized homopolymerpolyethylene gel (AC629A polyethylene from Allied-Signal Inc.) andethylene acrylic acid ionomer, preferably sodium ionomer (trademarkAclyn A 276 from Allied signal). The shell wall materials is heated attemperature just above their softening point (i.e. 140°-150° C.). Theheating is accompanied with constant mixing until all the ingredientsare melted and dissolved in the carrier soybean oil. At this stage thepigment, such as magnetic iron oxide pigment, i.e. the capsules corematerials, is added portion-wise to the hot shell wall materials whilemaintaining the constant stirring. After the completion of the additionof the iron oxide pigment, the mixture is allowed to be mixed until ahomogeneous, uniform dispersion of the iron oxide pigments in the hosthot shell wall forming materials is achieved. Finally the mixture isallowed to cool to the room temperature. Upon cooling the system, theshell wall materials solidify and encapsulate the particles, such asmagnetic powders, with a hydrophobic shell. An alkali blue may be addedto the iron oxide core materials to improve the color of the printedink.

The percentage compositions of the encapsulated iron oxide pigment wereas follows in Example I:

    ______________________________________                                        Soybean Oil        13.4%                                                      Beckacite XR4503 rosin                                                                           4.0%                                                       AC 629A polyethylene                                                                             2.5%                                                       Aclyn 276A         1.0%                                                       Iron Oxide pigment 80.0                                                       Alkaline Blue pigment                                                                            1.5%                                                       ______________________________________                                    

Other compositions were similarly prepared in the same general mannerwith the components as shown in Table I.

The encapsulated pigment prepared as mentioned above was thenincorporated in the ink vehicle to produce printing inks, such asmagnetic printing inks. An example of making the magnetic printing inkis described below:

The encapsulated pigment, from the above example, is added to alithographic ink vehicle in the proportion stated below: The ink vehiclewas made from 16-V-10 varnish (Sun Chemical), varnish #4895 (100% solidvarnish made from hydrocarbon resin, Superior Varnish), varnish #5848(100% solid soya gel varnish, Superior Varnish Co.). The mixture wasthen allowed to mix using a SCHOLD mixer for 2 hours. The resultantlithographic offset magnetic inks exhibit an excellent transfer, veryfast drying, high signal strength at thinner ink film, good adhesion andexcellent print quality, long run stability without emission of anyhazardous solvent.

The percentage composition of the offset magnetic ink are:

    ______________________________________                                        Encapsulated iron oxide pigment                                                                    77.5%                                                    16-V-10 Varnish      12.5%                                                    Varnish #4895        5.0%                                                     Varnish #5848        5.0%                                                     ______________________________________                                    

Several other formulations of the magnetic ink composition andcomparative compositions were made in the same general manner (Examples2-11) and are listed in Table I, along with the results of theirevaluation in standard lithographic printing, as shown in Table II,(Examples 12-34). The invention is not limited to this particular rangeof tack and viscosity. By modifying the percentage and the compositionof the shell wall materials, as well as the percentage and thecomposition of the ink vehicle. Inks with very wide range of tack andviscosity, can be produced, which can fit all existing printingtechnologies (impact as well as non-impact). It is desired that the inksexhibit a viscosity from about 200 to about 500, preferably from 300 to500 poises at 25° C., a tack of about 10 to about 35, preferably from 11to 25, and a fineness of grind ("FOG") of 0. Signal strength should behigh at the lowest possible ratchet setting, the higher ratchet settingbeing an indication of the need to deposit more ink onto the ink rollersand accordingly on the substrate. The encapsulated particles of Examples2 and 4 are used in the inks of Examples 12-14 and the inks of Example15, respectively. These particles do not contain an ionomer and thusperform less satisfactory than the particles containing the ionomer.However, such particles are still preferred over conventional particles.

In Table III, Examples 35 and 36, there is shown the production ofencapsulated pigments in accordance with the present invention in whichthe shell wall material uses a soya oil component to encapsulate coloredpigments.

In Table IV, Example 37, there is shown the production of a printing inkthat incorporates the encapsulated pigments made in accordance with theExample 35, in a carrier vehicle that incorporates a soya oil component.

In Table V, Examples 38-45, there is shown the production ofencapsulated carbon black in accordance with the present invention inwhich the shell wall material uses a soya oil component to encapsulatecolored pigments. Examples 39-41 and 43-45 also employ an ionomer in theshell wall. The encapsulated carbon black made with the use of ionomersis preferred to obtain the optimum functional properties in the inksmade therewith. The inks made with use of encapsulated pigments that donot contain ionomers (Examples 38 and 42--encapsulated pigments;Examples 46-47 and 60--inks) are still preferred over conventional inks.

In Table VI, Example 46-60, there is shown the production of printinginks that incorporate the encapsulated carbon blacks of Examples 38-45in carrier vehicles that incorporate soya oil components.

                  TABLE I                                                         ______________________________________                                        Ingredients          %                                                        ______________________________________                                        Example 2                                                                     Soybean Oil (Kerely) 13.50                                                    Maleic modified rosin, ester                                                                       4.30                                                     (Becacite XR 4503 - Arizona                                                   Chemical Co.)                                                                 PE 629A - oxidized   1.00                                                     polyethylene homopolymer                                                      (AC 629 - Allied signal)                                                      Iron Oxide - black magnetic                                                                        81.20                                                    ink pigment (031182 -                                                         Wright Industries)                                                            Example 3                                                                     Soybean Oil (Kerely) 21.80                                                    (Becacite XR 4503 - Arizona                                                                        6.90                                                     Chemical Co.)                                                                 PE 629A - oxidized   5.00                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 Magnox 353 (accicular iron                                                                         66.30                                                    oxide - Magnox Co.)                                                           Example 4                                                                     Soybean Oil (Kerely) 14.50                                                    AC 629A - oxidized   4.00                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 Iron Oxide (031182 - Wright                                                                        81.50                                                    Industries)                                                                   Example 5                                                                     Soybean Oil (Kerely) 13.50                                                    (Becacite XR 4503 - Arizona                                                                        4.20                                                     Chemical Co.)                                                                 AC629A - oxidized    1.00                                                     polyethylene homopolymer                                                      Allied Signal                                                                 AClyn 201 (calcium   0.30                                                     ionomer - Allied Signal)                                                      Iron Oxide (pigment  81.00                                                    031182 - Wright Industries)                                                   Example 6                                                                     Soybean Oil (Kerely) 13.50                                                    (Becatite XR 4503 - Arizona                                                                        4.20                                                     Chemical Co.)                                                                 AC 629A - oxidized   0.85                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 AClyn 276A (sodium   0.15                                                     ionomer - Allied Signal)                                                      Iron Oxide (pigment  81.30                                                    031182 - Wright Industries)                                                   Example 7                                                                     Soybean Oil (Kerely) 13.30                                                    (Becatite XR 4503 - Arizona                                                                        4.20                                                     Chemical Co.)                                                                 AC 629A - oxidized   0.83                                                     polyethylene homopolymer                                                      Allied Signal                                                                 AClyn A 276 (sodium ionomer                                                                        0.17                                                     Allied Signal)                                                                Iron Oxide (pigment  81.50                                                    031182 - Wright Industries)                                                   Example 8                                                                     Soybean Oil (Kerely) 13.34                                                    (Becatite XR 4503 - Arizona                                                                        4.00                                                     Chemical Co.)                                                                 AC 629A - oxidized   0.83                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 AClyn A 276 (sodium ionomer                                                                        0.33                                                     Allied Signal)                                                                Alkali Blue Pigment  1.50                                                     NB S6255D (BASF)                                                              Iron Oxide (pigment  80.00                                                    031182 - Wright Industries                                                    Example 9                                                                     Soybean Oil (Kerely) 13.34                                                    (Becatite XR 4503 - Arizona                                                                        4.00                                                     Chemical Co.)                                                                 AC 629A - oxidized   0.80                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 Aclyn 285A (sodium   0.17                                                     ionomer - Allied Signal)                                                      AClyn 276A (sodium   0.17                                                     ionomer - Allied Signal)                                                      Alkali Blue pigment - NB                                                                           1.50                                                     56255D - BASF                                                                 Iron Oxide pigment 031182 -                                                                        80.00                                                    Wright Industries                                                             Example 10 (identical to)                                                     Example 8)                                                                    Soybean Oil (Kerely) 13.33                                                    (Becatite XR 4503 - Arizona                                                                        4.00                                                     Chemical Co.)                                                                 AC 629A - oxidized   0.84                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 AClyn 276A (sodium   0.33                                                     ionomer - Allied Signal)                                                      Alkali Blue pigment - NB                                                                           1.50                                                     56255D - BASF                                                                 Iron Oxide (pigment  80.00                                                    031182 - Wright Industries)                                                   Example 11 (identical to                                                      Example 8)                                                                    Soybean Oil (Kerely) 13.33                                                    (Becatite XR 4503 - Arizona                                                                        4.00                                                     Chemical Co.)                                                                 AC 629A - oxidized   0.84                                                     polyethylene homopolymer -                                                    Allied Signal                                                                 AClyn 276A (sodium   0.33                                                     ionomer - Allied Signal)                                                      Alkali Blue pigment - NB                                                                           1.50                                                     56255D - BASF                                                                 Iron Oxide (pigment  80.00                                                    031182 - Wright Industries)                                                   ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Ink       %       Ink's                                                       Ingredients                                                                             Comp.   Physicals Press Evaluation                                  ______________________________________                                        Example 12                                                                    Pigment (Ex. 2)                                                                         68.00   Tack = 20.8                                                 16-V-10.sup.1                                                                           20.00   Vis = 468 Passed                                            Soy #6727.sup.2                                                                         10.00   FOG = 0   Water log test                                    Alkali Blue.sup.3                                                                       2.0               (10,000 copies)                                                               Passed                                            Example 13                                                                    Pigment (Ex. 2)                                                                         68.00   Tack = 18.4                                                                             Water Log (10000) =                               Soy Extender                                                                            8.00    Vis = 362 Passed                                            16-V-10.sup.1                                                                           15.00   FOG = 0                                                     Soy #6727.sup.2                                                                         7.00                                                                Alkali Blue.sup.3                                                                       2.00                                                                Example 14                                                                    Pigment (Ex. 2)                                                                         75.00   Tack = 22.8                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           18.00   Vis = 436 Passed                                            Soy #6726.sup.2                                                                         7.00    FOG = 0   Aquamatic Setting = 17                            Clayton AF.sup.4                                                                        0.50              Ratchet Setting = 3                                                           Signal Strength = 99%-109%                        Example 15                                                                    Pigment (Ex. 4)                                                                         75.00   Tack = 23.4                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           18.00   Vis = 501 Passed                                            Soy #6727.sup.2                                                                         7.0     FOG = 0   Aqua Setting = 20                                                             Ratchet Setting = 4                                                           Signal Strength = 96%-77%                         Example 16                                                                    Pigment (Ex. 6)                                                                         75.00   Tack = 16.7                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           12.50   Vis = 402 Passed                                            6848.sup.6                                                                              7.50    FOG = 0   Ratchet Setting = 2                               6849.sup.7                  Aquamatic Setting = 20                                                        Signal Strength = 105-106                         Example 17                                                                    Pigment (Ex. 6)                                                                         75.00   Tack = 18.6                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           15.00   Vis = 319 Passed                                            Soy Disp #6727                                                                          10.00   FOG = 0   Ratchet Setting = 2                                                           Aqua Setting = 20                                                             Signal Strength = 105-106                         Example 18                                                                    Pigment (Ex. 6)                                                                         75.00   Tack = 17.5                                                                             Water Log (10000) =                               SVD 2023.sup.8                                                                          15.00   Vis = 412 Passed                                            6848.sup.7                                                                              5.00    FOG = 0   Ratchet Setting = 2                               6849.sup.7                                                                              5.00              Aquamatic Setting = 18                            Soy Oil (Kerely)                                                                        1.00              Signal Strength = 106-96                          Example 19                                                                    Pigment (Ex. 6)                                                                         77.50   Tack = 14.7                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 460 Passed                                            6848.sup.6                                                                              7.50    FOG = 0   Ratchet Setting = 2                               6849.sup.7                                                                              5.00              Aquamatic Setting = 17                                                        Signal Strength = 107-148                         Example 20                                                                    Pigment (Ex. 6)                                                                         77.50   Tack = 19.8                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 415 Passed                                            Soy Disp #6727.sup.2                                                                    7.50    FOG = 0   Ratchet Setting = 2                                                           Aqua Setting = 17                                                             Signal Strength = 97-101                          Example 21                                                                    Pigment (Ex. 7)                                                                         77.50   Tack = 18 Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 483 Passed                                            6848.sup.6                                                                              5.00    FOG = 0   Ratchet Setting = 2                               6849.sup.7                                                                              5.00              Aquamatic Setting = 23                                      2.50              Signal Strength = 108-117                         Examle 22                                                                     Pigment (Ex. 7)                                                                         77.50   Tack = 19.1                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 343 Passed                                            4895.sup.10                                                                             5.00    FOG = 0   Ratchet Setting = 2-1                             Soy Disp #6727.sup.2                                                                    5.00              Aquamatic Setting = 23                            Alkali Blue.sup.9                                                                       2.50              Signal Strength = 105%-110%                       Example 23                                                                    Pigment (Ex. 7)                                                                         77.50   Tack = 17.0                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 496 Passed                                            6848.sup.6                                                                              5.00    FOG = 0                                                     6849.sup.7                                                                              5.00                                                                Alkali Blue.sup.9                                                                       2.50                                                                Example 24                                                                    Pigment (Ex. 7)                                                                         77.50   Tack = 17.1                                                                             Water Log (10000) =                               SVD 2023.sup.8                                                                          12.50   Vis = 409 Passed                                            4895.sup.10                                                                             2.50    FOG = 0   Ratchet Setting = 2.1                             6848.sup.6                                                                              5.00              Aquamatic Setting = 23                            Alkali Blue.sup.9                                                                       2.50              Signal Strenght = 105%-108%                       Example 25                                                                    Pigment (Ex. 7)                                                                         75.00   Tack = 15.4                                                                             Water Log (10000) =                               Ultrex 47.sup.12                                                                        12.50   Vis = 357 Passed                                            Ultrex 49.sup.13                                                                        10.00   FOG = 0   Ratchet Setting = 2-1                             Alkali Blue.sup.11                                                                      2.50              (mega = 3-2)                                                                  Aquamatic Setting = 17-19                                                     (mega 25-29)                                                                  Signal Strength =                                                             105/112%-100/109%                                 Example 26                                                                    Pigment (Ex. 8)                                                                         80.00   Tack = 13.7                                                                             Water Log (10000) =                               Ultrex 47.sup.12                                                                        10.00   Vis = 367 Passed                                            Ultrex 49.sup.13                                                                        10.00   FOG = 1   Aqua Setting = 20                                                             Signal Strength = 105%-111%                       Example 27                                                                    Pigment (Ex. 7)                                                                         77.50   Tack = 16.6                                                                             Water Log (10000) =                               SVD 2023.sup.8                                                                          10.00   Vis = 466 Passed                                            6848.sup.6                                                                              5.00    FOG = 0                                                     6849.sup.7                                                                              5.00                                                                Alkali Blue.sup.11                                                                      2.50                                                                Example 28                                                                    Pigment (Ex. 7)                                                                         77.50   Tack = 12 Water Log (10000) =                               6848.sup.6                                                                              5.00    Vis = 318 Passed                                            6849.sup.7                                                                              5.00    FOG = 0                                                     Alkali Blue                                                                             2.50                                                                Example 29                                                                    Pigment (Ex. 8)                                                                         80.00   Tack = 15 Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 406 Passed                                            6848.sup.6                                                                              5.00    FOG = 0                                                     6849.sup.7                                                                              5.00                                                                Example 30                                                                    Pigment (Ex. 7)                                                                         77.50   Tack = 14.7                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           10.00   Vis = 366 Passed                                            6848.sup.6                                                                              5.00    FOG = 0                                                     6849.sup.7                                                                              5.00                                                                Alkali Blue.sup.11                                                                      2.50                                                                Example 31                                                                    Pigment (Ex. 8)                                                                         80.00   Tack = 14.7                                                                             Water Log (10000) =                               Ultrex 47.sup.12                                                                        15.00   Vis = 366 Passed                                            Ultrex 49.sup.13                                                                        5.00    FOG = 0                                                     Example 32                                                                    Pigment (Ex. 9)                                                                         80.00   Tack = 15.3                                                                             Water Log (10000) =                               Ultrex 47.sup.12                                                                        15.00   Vis = 395 Passed                                            Ultrex 49.sup.13                                                                        5.00    FOG = 0                                                     Example 33                                                                    Pigment (Ex. 9)                                                                         80.00   Tack = 16.5                                                                             Water Log (10000) =                               16-V-10.sup.1                                                                           116.50  Vis = 307 Passed                                            4895.sup.10                                                                             3.50    FOG = 0                                                     Example 34                                                                    Pigment (Ex. 11)                                                                        77.50   Tack = 16.8                                                                             Water log test                                    16-V-10.sup.1                                                                           12.50   Vis = 373 (10,000 copies)                                   6848.sup.6                                                                              5.00    FOG = 0   Passed                                                      5.00                                                                ______________________________________                                         .sup.1 Varnish 16V-10 (General Printing Ink Co.)                              .sup.2 Soy Dispersion Varnish #6727 (Superior Varnish & Drier Co.)            .sup.3 Flushed Alkali blue R FL16-435 (PMC Specialties Group, Inc.)           .sup.4 Oregano clay Clayton AF (ECC International)                            .sup.5 20858 soy extender varnish (Kerely ink)11Quickset Alkali Blue          62QR-0856 (BASF)                                                              .sup.6 Varnish #6848, 100% solid Quickset soy gel (Superior)                  .sup.7 Varnish #6849, 100% solid soya gloss varnish (Superior)                .sup.8 Varnish #SVD 2023 (Superior)12Ulterax 47  soya varnish  Lawter         International                                                                 .sup.9 Flush alkali blue R, FL16-435 (PMC, Inc.)                              .sup.10 Varnish #4895 (100% solid soy varnish  Superior)                      .sup.11 Quickset Alkali Blue 62QR-0856 (BASF)                                 .sup.12 Ulterax 47  soya varnish  Lawter International                        .sup.13 Ulterax 49  soya varnish  Lawter International                   

                  TABLE III                                                       ______________________________________                                        Ingredients            %                                                      ______________________________________                                        Example 35                                                                    Soy Bean Oil (Kerely)  38.72                                                  Maleic modified rosin ester                                                                          12.10                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene homopolymer                                                                    5.80                                                   (Allied Signal - AC629)                                                       Sunperse Rubine 57:1 pigment                                                                         43.38                                                  (Sun Chemical 219-0026)                                                       Example 36                                                                    Soy Bean Oil (Kerely)  40.00                                                  Maleic modified rosin ester                                                                          14.00                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene homopolymer                                                                    6.00                                                   (Allied signal - AC629)                                                       Alkali Blue (BASF 0147-4008)                                                                         40.00                                                  ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        Ingredients              %                                                    ______________________________________                                        Example 37                                                                    Encapsulated Rubine Pigment (Example 35)                                                               50.00                                                Soy Dispersion Varnish #6727 (Superior                                                                 10.00                                                Varnish & Drier Co.)                                                          Varnish 16-V-10 (General Printing Ink Co.)                                                             25.00                                                Soy Bean Extender #20658 (Kerely Ink)                                                                  5.00                                                 Polyethylene wax S-394-N1 (Shamrock                                                                    2.00                                                 Technologies Inc.)                                                            Polytetrafluoroethylene PTFE SST-3P                                                                    1.00                                                 (Shamrock Technologies Inc.)                                                  Cup Grease #3 (Magie Brother)                                                                          3.00                                                 Tocopherol COVI-OX T70 (Henkel                                                                         0.50                                                 Corporation)                                                                  Organo Clay Clayton AF (ECC                                                                            1.00                                                 International)                                                                Soy Bean Oil (Kerely Inc.)                                                                             2.50                                                 ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        Ingredients          %                                                        ______________________________________                                        Example 38                                                                    Soy Bean Oil (Kerely)  40.00                                                  Maleic modified rosin ester                                                                          14.00                                                  (Arizona - Beckacite XR4503)                                                  Polyethylene homopolymer                                                                             6.00                                                   (Allied Signal - A617)                                                        Carbon Black           36.00                                                  (Mogul L, Cabot Corp.)                                                        Alkali Blue pigment    4.00                                                   (BASF - 0147-4008)                                                            Example 39                                                                    Soy Bean Oil (Kerely)  40.00                                                  Maleic modified rosin ester                                                                          12.00                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene  3.00                                                   homopolymer (Allied Signal -                                                  AC629)                                                                        Ethylene Acrylic acid calcium                                                                        1.00                                                   ionomer (Allied Signal Aclyn                                                  201)                                                                          Carbon Black           44.00                                                  (Cabot, Mogul L)                                                              Example 40                                                                    Soy Bean Oil (Kerely)  40.00                                                  Maleic modified rosin ester                                                                          10.00                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethlylene 3.00                                                   homopolymer (Allied Signal -                                                  AC629)                                                                        Ethylene Acrylic acid calcium                                                                        0.10                                                   ionomer (Allied Signal Aclyn                                                  201)                                                                          Carbon Black           40.00                                                  (Cabot, Mogul L)                                                              Pigment Blue 27 (Manox-Manox)                                                                        6.90                                                   blue 2MD)                                                                     Example 41                                                                    Soy Bean Oil (Kerely)  40.00                                                  Maleic modified rosin ester                                                                          10.00                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene  5.50                                                   homopolymer (Allied Signal -                                                  AC629                                                                         Ethylene Acrylic acid calcium                                                                        0.50                                                   ionomer (Allied Signal Aclyn                                                  201)                                                                          Carbon Black           44.00                                                  (Cabot, Mogul L)                                                              Example 42                                                                    Soy Bean Oil (Kerely)  43.00                                                  Maleic modified rosin ester                                                                          10.75                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene  3.25                                                   homopolymer (Allied Signal -                                                  AC629                                                                         Carbon Black           43.00                                                  (Cabot, Mogul L)                                                              Example 43                                                                    Soy Bean Oil (Kerely)  41.70                                                  Maleic modified rosin ester                                                                          10.40                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene  5.70                                                   homopolymer (Allied Signal -                                                  AC629                                                                         Ethylene Acrylic acid calcium                                                                        0.50                                                   ionomer (Allied Signal -                                                      Aclyn 276A)                                                                   Carbon Black           41.70                                                  (Cabot, Mogul L)                                                              Example 44                                                                    Soy Bean Oil (Kerely)  41.70                                                  Maleic modified rosin ester                                                                          10.40                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene  5.70                                                   homopolymer (Allied Signal -                                                  AC629                                                                         Ethylene Acrylic acid calcium                                                                        0.50                                                   ionomer (Allied Signal -                                                      Aclyn 285A)                                                                   Carbon Black           41.70                                                  (Cabot, Mogul L)                                                              Example 45                                                                    Soy Bean Oil (Kerely)  40.00                                                  Maleic modified rosin ester                                                                          15.00                                                  (Arizona - Beckacite XR4503)                                                  Oxidized polyethylene  2.50                                                   homopolymer (Allied Signal -                                                  AC629                                                                         Ethylene Acrylic acid calcium                                                                        0.50                                                   ionomer (Allied Signal -                                                      Aclyn 276A)                                                                   Carbon Black           42.00                                                  (Cabot, Mogul L)                                                              ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        Ingredients                  %                                                ______________________________________                                        Example 46                                                                    Encapsulated Carbon Black (Example 38)                                                                     45.00                                            Quickset Gel Miracle Gel #6684                                                                             15.00                                            (Superior Varnish & Drier Co.)                                                Varnish 16-V-10 (General Printing Ink Co.)                                                                 20.00                                            Soy Dispersion Varnish #6727 9.50                                             (Superior Varnish & Drier Co.)                                                Tocopherol COVI-OX T70       0.50                                             (Henkel Corporation)                                                          Magnesium Silicate (Wittaker Inc.)                                                                         4.00                                             Organophilic Clay Bentone 500 (NL                                                                          1.00                                             Chemicals)                                                                    Polyethylene wax S-394-N1    2.00                                             (Shamrock Technologies Inc.)                                                  Polytetrafluoroethylene PTFE SST-3P                                                                        1.00                                             (Shamrock Technologies Inc.)                                                  Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 47                                                                    Encapsulated Carbon Black (Example 38)                                                                     45.00                                            Soy Dispersion Varnish #6727 10.00                                            (Superior Varnish & Drier Co.)                                                Soy Extender #20658 (Kerely Inc.)                                                                          12.50                                            Varnish 16-V-10 (General Printing Ink Co.)                                                                 20.00                                            Soy Varnish Ultrex 47        11.00                                            (Lawter International)                                                        Polytetrafluoroethylene PTFE SST-3P                                                                        1.00                                             (Shamrock Technologies Inc.)                                                  Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Example 48                                                                    Encapsulated Carbon Black (Example 45)                                                                     45.50                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        3.00                                             Milori Blue FL-17-654 (PMC Inc.)                                                                           2.00                                             Varnish SVD 2023             20.00                                            (Superior Varnish & Drier Co.)                                                Quickset Soya Gel #6848      10.00                                            (Superior Varnish & Drier Co.)                                                Grinding Vehicle #4895       10.00                                            (Superior Varnish & Drier Co.)                                                Cup Grease #3                2.00                                             Polyethylene wax S-394-N1    3.00                                             (Shamrock Technologies Inc.)                                                  Polytetrafluoroethylene PTFE SST-3P                                                                        1.50                                             (Shamrock Technologies Inc.)                                                  Hydrophobic fumed silica, Aerosil R972                                                                     1.00                                             (Degussa)                                                                     Tridecyl Alcohol Exal 13 (Exxon Corp.)                                                                     1.00                                             Soy Beam Oil (Kerely Inc.)   1.00                                             Example 49                                                                    Encapsulated Carbon Black (Example 39)                                                                     48.50                                            Quickset Gel Miracle Gel #6684                                                                             15.00                                            (Superior Varnish & Drier Co.)                                                Varnish 16-V-10 (General Printing Ink Co.)                                                                 20.00                                            Soy Dispersion Varnish #6727 10.00                                            (Superior Varnish & Drier Co.)                                                Organophilic Clay Bentone 500                                                                              1.00                                             (NL Chemicals)                                                                Polyethylene wax S-394-N1    2.00                                             (Shamrock Technologies Inc.)                                                  Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Polytetrafluoroethylene PTFE SST-3P                                                                        1.00                                             (Shamrock Technologies Inc.)                                                  Cup Grease #3 (Magie brother)                                                                              2.00                                             Example 50                                                                    Encapsulated Carbon Black (Example 39)                                                                     52.38                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        4.76                                             Quickset Gel Miracle Gel #6684                                                                             16.19                                            (Superior Varnish & Drier Co.)                                                Soy Dispersion Varnish #6727 9.52                                             (Superior Varnish & Drier Co.)                                                Varnish 16-V-10              10.95                                            (General Printing Ink Co.)                                                    Organophilic Clay Bentone 500                                                                              1.90                                             (NL Chemicals)                                                                Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.48                                             Cup Grease #3 (Magie Brother)                                                                              1.90                                             Soy Bean Oil (Kerely Ink)    1.90                                             Example 51                                                                    Encapsulated Carbon Black (Example 39)                                                                     55.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        5.00                                             Quickset Gel Miracle Gel #6684                                                                             15.00                                            (Superior Varnish & Drier Co.)                                                Soy Dispersion Varnish #6727 10.00                                            (Superior Varnish & Drier Co.)                                                Quickset Varnish Snapset #6367                                                                             11.50                                            (Superior Varnish & Drier Co.)                                                Organophilic Clay Bentone 500                                                                              1.00                                             (NL Chemicals)                                                                Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 52                                                                    Encapsulated Carbon Black (Example 40)                                                                     45.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        4.50                                             Quickset Gel Miracle Gel #6684                                                                             13.00                                            (Superior Varnish & Drier Co.)                                                Soy Dispersion Varnish #6727 9.00                                             (Superior Varnish & Drier Co.)                                                Varnish 16-V-10              18.00                                            (General Printing Ink Co.)                                                    Organophilic Clay Bentone 500                                                                              0.90                                             (NL Chemicals)                                                                Magnesium Silicate (Wittaker Inc.)                                                                         2.70                                             Polytetrafluoroethylene PTFE SST-3P                                                                        0.90                                             (Shamrock Technologies Inc.)                                                  Soy Bean Oil (Kerely Inc.)   2.70                                             Kodaflex TX1B Plasticizer    1.00                                             (Eastman Chemicals)                                                           Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 53                                                                    Encapsulated Carbon Black (Example 40)                                                                     49.02                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        3.92                                             Quickset Gel Miracle Gel #6684                                                                             9.80                                             (Superior Varnish & Drier Co.)                                                Soy Dispersion Varnish #6727 11.76                                            (Superior Varnish & Drier Co.)                                                Varnish 16-V-10 (General Printing Ink Co.)                                                                 14.71                                            VersaFlow (Shamrock Technologies Inc.)                                                                     0.49                                             Hydrophobic fumed silica, Aerosil R972                                                                     0.98                                             (Degussa)                                                                     Polytetrafluoroethylene PTFE SST-3P                                                                        0.98                                             (Shamrock Technologies Inc.)                                                  Soy Bean Oil (Kerely Inc.)   3.92                                             Kodaflex TX1B Plasticizer    0.98                                             (Eastman Chemicals)                                                           Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.49                                             Cup Grease #3 (Magie Brother)                                                                              2.94                                             Example 54                                                                    Encapsulated Carbon Black (Example 40)                                                                     43.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.00                                             Pigment Blue 27, Manox blue (Manox                                                                         3.00                                             Corporation)                                                                  Quickset Varnish Snapset #6367                                                                             25.00                                            (Superior Varnish & Drier Co.)                                                Quickset Gel Miracle Gel #6684                                                                             5.00                                             (Superior Varnish & Drier Co.)                                                Soy Dispersion Varnish #6727 15.00                                            (Superior Varnish & Drier Co.)                                                Oil base dispersion vehicle 100-SXL                                                                        2.00                                             (Lawter International)                                                        Organophilic Clay Bentone 500                                                                              0.50                                             (NL Chemicals)                                                                Polytetrafluoroethylene PTFE SST-3P                                                                        1.00                                             (Shamrock Technologies Inc.)                                                  Kodaflex TX1B Plasticizer    1.00                                             (Eastman Chemicals)                                                           Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 55                                                                    Encapsulated Carbon Black (Example 41)                                                                     41.03                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.05                                             Pigment Blue 27, Manox blue 2MD                                                                            3.08                                             (Manox Corporation)                                                           Varnish 16-V-10 (General Printing Ink Co.)                                                                 20.51                                            Soy Dispersion Varnish #6727 10.26                                            (Superior Varnish & Drier Co.)                                                Soy Extender #20658 (Kerely Inc.)                                                                          10.26                                            Quickset Gel Miracle Gel #6684                                                                             10.26                                            (Superior Varnish & Drier Co.)                                                Organophilic Clay Bentone 500                                                                              0.51                                             (NL Chemicals)                                                                Cup Grease #3 (Magie Brother)                                                                              2.05                                             Example 56                                                                    Encapsulated Carbon Black (Example 41)                                                                     40.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.00                                             Pigment Blue 27, Manox blue 2MD                                                                            2.50                                             (Manox Corporation)                                                           Varnish 16-V-10 (General Printing Ink Co.)                                                                 20.00                                            Soy Dispersion Varnish #6727 12.00                                            (Superior Varnish & Drier Co.)                                                Soy Extender #20658 (Kerely Inc.)                                                                          10.00                                            Quickset Gel Miracle Gel #6684                                                                             10.00                                            (Superior Varnish & Drier, Co.)                                               Tridecyl Alcohol, Exal 13 (Exxon                                                                           1.00                                             Corporation)                                                                  Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Kodaflex TX1B Plasticizer    1.00                                             (Eastman Chemicals)                                                           Soy Bean Oil (Kerely Ink)    1.00                                             Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 57                                                                    Encapsulated Carbon Black (Example 41)                                                                     40.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.00                                             Pigment Blue 27, Manox blue 2MD                                                                            2.00                                             (Manox Corporation)                                                           Varnish 16-V-10 (General Printing Ink Co.)                                                                 20.00                                            Soy Dispersion Varnish #6727 15.00                                            (Superior Varnish & Drier Co.)                                                Soy Extender #20658 (Kerely Inc.)                                                                          10.00                                            Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Tridecyl Alcohol, Exal 13    1.00                                             (Exxon corporation)                                                           Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 58                                                                    Encapsulated Carbon Black (Example 43)                                                                     45.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.00                                             Pigment Blue 27, Manox blue 2MD                                                                            3.00                                             (Manox Corporation)                                                           Varnish 16-V-10 (General Printing Ink Co.)                                                                 18.50                                            Soy Dispersion Varnish #6727 15.00                                            (Superior Varnish & Drier Co.)                                                Quickset Gel Miracle Gel #6684                                                                             10.00                                            (Superior Varnish & Drier Co.)                                                Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Organophilic Clay Bentone 500                                                                              1.00                                             (NL Chemicals)                                                                Smoother Compound (AB Dick, 3-8100)                                                                        2.00                                             Tridecyl Alcohol, Exal 13    1.00                                             (Exxon Corporation)                                                           Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 59                                                                    Encapsulated Carbon Black (Example 44)                                                                     45.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.00                                             Pigment Blue 27, Manox blue 2MD                                                                            3.00                                             (Manox Corporation)                                                           Varnish 16-V-10 (General Printing Ink Co.)                                                                 18.50                                            Soy Dispersion Varnish #6727 15.00                                            (Superior Varnish & Drier Co.)                                                Quickset Gel Miracle Gel #6684                                                                             10.00                                            (Superior Varnish & Drier Co.)                                                Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Organophilic Clay Bentone 500                                                                              1.00                                             (NL Chemicals)                                                                Smoother Compound (AB Dick, 3-8100)                                                                        2.00                                             Tridecyl Alcohol, Exal 13    1.00                                             (Exxon Corporation)                                                           Cup Grease #3 (Magie Brother)                                                                              2.00                                             Example 60                                                                    Encapsulated Carbon Black (Example 42)                                                                     45.00                                            Alkali Blue Flush 62-QR-0856 (BASF)                                                                        2.00                                             Pigment Blue 27, Manox blue 2MD                                                                            3.00                                             (Manox Corporation)                                                           Varnish 16-V-10 (General Printing Ink Co.)                                                                 18.50                                            Soy Dispersion Varnish #6727 15.00                                            (Superior Varnish & Drier Co.)                                                Quickset Gel Miracle Gel #6684                                                                             10.00                                            (Superior Varnish & Drier Co.)                                                Tocopherol COVI-OX T70 (Henkel Corporation)                                                                0.50                                             Organophilic Clay Bentone 500                                                                              1.00                                             (NL Chemicals)                                                                Smoother Compound (AB Dick, 3-8100)                                                                        2.00                                             Tridecyl Alcohol, Exal 13    1.00                                             (Exxon Corporation)                                                           Cup Grease #3 (Magie Brother)                                                                              2.00                                             ______________________________________                                    

    ______________________________________                                        CARBON BLACK                                                                         Example #                                                              Ingredients                                                                            38     39     40   41   42   43   44   45                            ______________________________________                                        Soy bean yes    yes    yes  yes  yes  yes  yes  yes                           oil                                                                           XR 4503  yes    yes    yes  yes  yes  yes  yes  yes                           Polyethyl-                                                                             yes    yes    yes  yes  yes  yes  yes  yes                           ene                                                                           Ionomer  no     yes    no   yes  no   yes  yes  yes                           Alkali Blue                                                                            yes    no     yes  no   no   no   no   no                            Carbon   yes    yes    yes  yes  yes  yes  yes  yes                           Black                                                                         Example No.                                                                            46     49     52   55   60   58   59   48                            of the Ink                                                                             47     50     53   56                                                                51     54   57                                                ______________________________________                                    

Significant improvement in the functional properties of the ink wasobserved when the encapsulated carbon black contained ionomers.

    ______________________________________                                        MAGNETIC                                                                      Example #                                                                     Ingredients                                                                           2      3     4    5   6    7   8    9   10   11                       ______________________________________                                        Soy bean oil                                                                          yes    yes   yes  yes yes  yes yes  yes yes  yes                      XR 4503 yes    yes   no   yes yes  yes yes  yes yes  yes                      Polyethylene                                                                          yes    yes   yes  yes yes  yes yes  yes yes  yes                      Ionomer no     no    no   yes yes  yes yes  yes yes  yes                      Alkali Blue                                                                           no     no    no   no  no   no  yes  yes yes  yes                      Iron Oxide                                                                            yes    yes   yes  yes yes  yes yes  yes yes  yes                      Example No.                                                                           12           15       16   22  26   32       34                       of the Ink                                                                            13                    17   23  27                                             14                    18   24  28                                                                   19   25  29                                                                   20   30  31                                                                   21                                              ______________________________________                                         Remarks                                                                       2Examples Nos. 8, 10 & 11 are also identical.                                 3Significant improvement in the ink's functional properties was observed      when the encapsulated iron oxide contains the ionomers and XR4503 resins.     4Ink's Physicals:                                                             Tack: was measured by an inkometer (from Thawing Albert) at 1200 RPM, 90      F., and after 1 min.                                                          Viscosity: was measured by Laray viscometer at 25 C.                          Finess of Grind was measured by precession grind gage                         5Press evaluation of the inks:                                                Water Log test: All inks were tested on A. B. Dick duplicator equipped        with either an integrated or segregated dampening system. The press was       operated at maximum speed of 9,000-10,000 copies per hour for a total of      10,000 copies.                                                                Signal strength: The magnetic strength of the magnetic inks was measured      using RDM MICR qualifier from research development & manufacturing            corporation.                                                                  Prints quality: All inks were tested on A. B. Dick duplicator and presses     using metal, silvermaster and maega plates and their corresponding            chemistry.                                                               

What is claimed is:
 1. A method for encapsulating particles selectedfrom the group consisting of magnetic particles and pigments having aparticle diameter from about 0.1 to about 100 microns, comprisingforming a melt by heating an ionomer and a hydrocarbon oil, dispersingsaid particles in said melt, and allowing said dispersion to cool, saidmelt being free of volatile organic solvents and said melt comprisingfrom about 10 to about 90 percent by weight of the encapsulated product.2. The method of claim 1 wherein said pigment is carbon black.
 3. Themethod of claim 1 wherein the melt also comprises a thixotropic agent.4. The method of claim 1 wherein the melt also comprises a binder resin.5. An encapsulation method comprising dispersing particles selected fromthe group consisting of magnetic particles and pigments having aparticle diameter from about 0.1 to about 100 microns in a fluid mediumthat comprises a hydrocarbon oil and components for forming a shell wallaround the particles, without the presence of any volatile organicsolvent, heating the resulting dispersion, and cooling the dispersion toallow the components of the medium to solidify to form the shell wall toencapsulate the particles.
 6. The method of claim 5 wherein the shellwall comprises from about 10 to about 80 percent, by weight, of thetotal weight of the encapsulated particle.
 7. The method of claim 6wherein the oil is a vegetable oil.
 8. The method of claim 7 wherein theshell wall comprises a thixotropic agent.
 9. The method of claim 2wherein the shell wall comprises a binder resin.
 10. The method of claim6 wherein the particle is a magnetic particle having a particle sizefrom about 0.5 to about 5.0 microns.
 11. The method of claim 5 whereinthe particle is carbon black.
 12. The method of claim 6 wherein theparticle is a pigment.
 13. A method for making an ink comprising:(1)forming encapsulated particles by dispersing particles selected from thegroup consisting of magnetic particles and pigments, having a particlediameter from about 0.1 to about 100 microns in a fluid medium thatcomprises the components for forming a shell wall around the particles,without the presence of any volatile organic solvent, heating theresulting dispersion, and cooling the dispersion to allow the componentsof the medium to solidify to form the shell wall to encapsulate theparticles; and (2) dispersing from about 10 to about 90 percent, byweight of the encapsulated particles in a printing ink vehicle.
 14. Themethod of claim 13 wherein the particles are magnetic particles having aparticle size from about 0.5 to about 5.0 microns.
 15. The method ofclaim 13 wherein the particles are carbon black.
 16. The method of claim13 wherein the particles are pigments.
 17. The method of claim 13wherein the printing ink vehicle is one suitable for lithographic,letterpress, gravure, or flexographic printing, or for use as aradiation curable ink.
 18. A method for encapsulating particles selectedfrom the group consisting of magnetic particles and pigments, having aparticle diameter from about 0.1 to about 100 microns, comprisingforming a melt by heating a hydrocarbon oil and a polymeric binder,dispersing said particles in said melt, and allowing said dispersion tocool, said melt being free of volatile organic solvents and said meltfrom about 10 to about 90 percent by weight of the encapsulated product.19. The method of claim 18 wherein said melt also comprises an ionomer.20. The method of claim 18 wherein the melt also comprises a thixotropicagent.
 21. The method of claim 18 wherein the oil is a vegetable oil.